CN106715737A - Device for fixing biological soft tissue, and method for producing same - Google Patents
Device for fixing biological soft tissue, and method for producing same Download PDFInfo
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- CN106715737A CN106715737A CN201580048143.2A CN201580048143A CN106715737A CN 106715737 A CN106715737 A CN 106715737A CN 201580048143 A CN201580048143 A CN 201580048143A CN 106715737 A CN106715737 A CN 106715737A
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- organism
- soft tissue
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- clamp
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- 238000004519 manufacturing process Methods 0.000 title 1
- 239000000956 alloy Substances 0.000 claims abstract description 86
- 229910000861 Mg alloy Inorganic materials 0.000 claims abstract description 69
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 35
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 33
- 210000001519 tissue Anatomy 0.000 claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims description 62
- 238000012545 processing Methods 0.000 claims description 38
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- 238000000034 method Methods 0.000 claims description 35
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- 239000011777 magnesium Substances 0.000 abstract description 41
- 229910052749 magnesium Inorganic materials 0.000 abstract description 27
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 26
- 238000001727 in vivo Methods 0.000 abstract description 16
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- 230000008878 coupling Effects 0.000 abstract 1
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- 230000000052 comparative effect Effects 0.000 description 31
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
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- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 2
- 239000004137 magnesium phosphate Substances 0.000 description 2
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- YIQKLZYTHXTDDT-UHFFFAOYSA-H Sirius red F3B Chemical compound C1=CC(=CC=C1N=NC2=CC(=C(C=C2)N=NC3=C(C=C4C=C(C=CC4=C3[O-])NC(=O)NC5=CC6=CC(=C(C(=C6C=C5)[O-])N=NC7=C(C=C(C=C7)N=NC8=CC=C(C=C8)S(=O)(=O)[O-])S(=O)(=O)[O-])S(=O)(=O)O)S(=O)(=O)O)S(=O)(=O)[O-])S(=O)(=O)[O-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] YIQKLZYTHXTDDT-UHFFFAOYSA-H 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
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- HLUCICHZHWJHLL-UHFFFAOYSA-N hematein Chemical compound C12=CC=C(O)C(O)=C2OCC2(O)C1=C1C=C(O)C(=O)C=C1C2 HLUCICHZHWJHLL-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/02—Inorganic materials
- A61L31/022—Metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C23/00—Extruding metal; Impact extrusion
- B21C23/002—Extruding materials of special alloys so far as the composition of the alloy requires or permits special extruding methods of sequences
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D7/00—Casting ingots, e.g. from ferrous metals
- B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Epidemiology (AREA)
- Public Health (AREA)
- Vascular Medicine (AREA)
- Heart & Thoracic Surgery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Surgery (AREA)
- Veterinary Medicine (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials For Medical Uses (AREA)
- Forging (AREA)
Abstract
The purpose of the present invention is to provide a device for fixing biological soft tissue, the device being composed of a magnesium-based alloy material, wherein the device is endowed with strength and deformation performance for being used as a device for coupling biological soft tissue that has been cut or separated due to an incision or the like during a surgical procedure, and is completely degraded in vivo and discharged after adhesion of the soft tissue or after healing of the incision tissue. This device, composed of a magnesium-based alloy material, is composed of a ternary Mg alloy material of Mg-Ca-Zn. In the Mg alloy material, the Ca and Zn are contained within the solid-solubility limit with respect to the Mg. The remainder is composed of Mg and unavoidable impurities. The Zn content is 0.5 at% or less. The Ca and Zn content has a relationship of Ca:Zn=1:x (where x is 1 to 3) by atom ratio. The crystal grain structure is equiaxed, the crystal grain size according to linear intercept being 30 to 250 [mu]m.
Description
Technical field
The present invention relates to the organism soft tissue fixation device using magnesium system alloy material.
Background technology
As conventional organism soft tissue fixation device, such as in the blood vessel clip of surgical operation, use titanium material etc.
Material stable in vivo.For the device using titanium material, healing in cut tissue, cure after not only without
With, and semi-permanently residue in vivo, thus in MRI (Magnetic Resonanse Imaging), X ray CT
When (Computed Tomography) shoots, (there is the strong metal for absorbing X-ray in measuring object as metal artifacts
Deng density high-selenium corn material high when, there is the phenomenon of artificial noise in the image for shooting) the reason for, exist to prognosis
Diagnosis etc. brings the problem of obstacle.
On the other hand, as organism must element magnesium due to high specific strength can be obtained from light weight, therefore as structure
Material attracts attention, and biocompatibility is excellent in addition, decomposability in performance bioagent, it is therefore contemplated that it is used as soft group of organism
Knit the material of fixation device.But, the ductility of pure magnesium is low, and device fracture is worried when soft tissue is fixed.
In nearest research, various magnesium systems alloy material is also being developed as the device material being decomposed in vivo
Material, but there is problems with：Fixed with the deformation performance of device as the organism soft tissue such as surgical operation clamp, stapler
It is not enough.
For example, as known magnesium system alloy material, it is known to contain Zn and rare earth element (RE in Mg：Gd, Tb, Tm
In more than a kind), the Mg alloy materials of the Mg-Zn-RE with long period stepped construction (with reference to patent document 1).But, it is dilute
There is problems with earth elements：It is expensive as material, additionally may act as morphotropism during organism soft tissue fixation device
Can be insufficient.
In addition, as known magnesium system alloy material, it is known to do not use rare earth element and it is cheap, by inanimate object body toxicity
The Mg alloy materials (with reference to patent document 2) that 3 yuan of the Mg-Ca-Zn that the element of problem is constituted are, because element addition is more,
Therefore worry that decomposition rate in vivo is fast.Magnesium system alloy material disclosed in patent document 2 is with the high intensity of magnesium
Purpose, not payes attention to the alloy of morphotropism, if average grain diameter is not below 1 μm in addition, cannot be formed as unique reinforcing
The periodic structure of tissue.
Here, the Mg alloy materials for being for 3 yuan of the Mg-Ca-Zn of the grain structure of 0.3~2 μm of average grain diameter are (as comparing
Example Mg alloy materials) characteristic, reference picture 24 and Figure 25 are illustrated.Figure 24 is represented for only implementing at 250 DEG C
Implement the hot-extrudable treatment of hot-extrudable processing and the material for making annealing treatment is not carried out, compression true stress-logarithmic strain relation
Performance diagram.Compression true stress-logarithmic strain relation corresponds to compressive strength-deflection.As the Mg alloys of comparative example
The content (atom %) that material has 4 kinds, the Ca and Zn of Mg alloy materials is recorded in the curve map of Figure 24 (1).Comparative example 1~
In the case of 4 Mg alloy materials, all of alloy occurs below fracture in logarithmic strain (True strain) 0.15, therefore
Can confirm that deformation performance is low.Show to be seen with transmission electron microscope for the Mg alloy materials of comparative example 4 in Figure 24 (2)
Examine the image for obtaining.The crystallization particle diameter that the Mg alloy materials of comparative example 4 are can confirm that by Figure 24 (2) is less than 1 μm.
Figure 25 is to represent implement the hot-extrudable treatment of hot-extrudable processing at 300 DEG C for only implementing, annealing is not carried out
It is material, compression true stress-logarithmic strain relation performance diagram.Compression true stress-logarithmic strain relation pair should
In compressive strength-deflection.The content (atom %) of the Ca and Zn of Mg alloy materials is identical with the curve map of Figure 24 (1).Than
In the case of Mg alloy materials compared with example 5~8, any alloy occurs below disconnected in logarithmic strain (True strain) 0.15
Split, thus it is confirmed that deformation performance is low.
In addition, according to magnesium system alloy material, existing and being not intended as principal component with the rising of the addition concentration of alloying element
There is dissolution and the problem of the ion of generation or the toxicity of compound occur in magnesium but addition element.In light of this situation,
Know there is following material：For a kind of metallic element as the second composition being added in Mg, only select organismal toxicity low
Element, do not make to be improved to more than required degree as the concentration of the element of second composition, without precipitate and intermetallic
Thing ensures as the function (with reference to patent document 3) of decomposability metal material in magnesium system organism.The magnesium system of patent document 3 closes
In golden material, element compound depended in organism for the toxicity of organism in concentration (amount), the element of addition is
Micro, then the possibility that toxicity occurs is reduced, therefore for having excluded the remaining unit of the clear and definite element of organismal toxicity
Element, the maximum concentration of the content of second composition is set as 1/3 or so of the solid solubility limit concentration in magnesium.
Also, compared with metallic radius small Au, Ag, Al, Zn etc., if addition metallic radius big Ca, Yb, Gd, In etc.,
Then constant decomposition rate reduction, in magnesium system alloy material, the species of the second element according to addition controls alloy material with amount
The corrosion resistance of material.
But, in the case that the second composition added in Mg is Zn, Ca as the necessary element of organism, its content need not set
It is set to 1/3 or so of the solid solubility limit concentration in magnesium.Additionally, in patent document 3,3 yuan of Mg for being for Mg-Ca-Zn
Alloy material does not have any disclosure.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2009-221579 publications
Patent document 2：International Publication pamphlet WO2013/069638
Patent document 3：No. 5333886 publications of Japanese Patent No.
The content of the invention
Invent problem to be solved
As described above, as the device material for decomposing in vivo, developing various magnesium systems alloy material, but there is use
Make the organism soft tissue such as surgical operation clamp, stapler to fix with the insufficient problem of the deformation performance of device.
In view of the situation, it is an object of the invention to provide a kind of organism soft tissue fixation device, it is closed by magnesium system
The device that golden material is constituted, possesses the organism soft tissue for being used as in surgical operation, being cut off or be separate by incision etc.
(internal organs, blood vessel etc.) conclude device intensity and deformation performance, and soft tissue healing after or cut tissue cure after,
It is completely broken down in organism and is discharged.
The means used to solve the problem
Zinc, the adding rate (amount) of calcium, the magnesium system alloy as the necessary element of organism for the addition in magnesium such as the present inventor
Preparation method in depth studied, as a result find, 3 yuan of Mg alloy material structures for being of the Mg-Ca-Zn with specific
Into device be useful as organism soft tissue fixation device.
That is, organism soft tissue fixation device of the invention is the device being made up of 3 yuan of the Mg-Ca-Zn Mg alloy materials for being
Part, on Mg alloy materials, Ca and Zn is contained within relative to Mg in solid solution limit, and surplus is by Mg and inevitable impurity
Constitute, the content of Zn is below 0.5 atom %, and the content of Ca and Zn is with atomic ratio measuring as Ca：Zn=1：X (wherein, x be 1~3)
Relation, the Mg alloy materials are by equi-axed crystal organizational composition that average crystallite particle diameter is 20~250 μm.
By the composition, possess as the intensity and deformation performance of organism soft tissue fixation device, and heal in soft tissue
It is completely broken down in vivo after conjunction or after cut tissue is cured.
Wherein understand, if the content of Zn is more than 0.5 atom %, the decomposition rate in organism accelerates, after embedment organism is interior,
Substantial amounts of gas is produced with decomposing, the reason for delay as organized renewing.Therefore, the content of Zn is controlled to 0.5 atom %
Below.If in addition, content of the content of Zn than Ca and Zn is with atomic ratio measuring Ca：Zn=1：1 is small, then presence cannot obtain necessity
Ductility problem.On the other hand, if the content of Zn compares Ca：Zn=1：3 is big, then in the presence of the decomposition rate for showing rapidly
Problem.
Organism soft tissue fixation device of the invention, by being made annealing treatment, so as to by average crystallite particle diameter be 20~
250 μm of equi-axed crystal organizational composition, is not only intensity raising and deformation performance is also improved.It should be noted that flat
Equal crystallization particle diameter is by the image of grain structure, by division lines method (original text：リ ニ ア イ ン タ ー セ プ ト methods) it is measured.
In addition, it is further preferred that organism soft tissue fixation device of the invention is by 3 yuan of the Mg-Ca-Zn Mg alloys for being
The device that material is constituted, on Mg alloy materials, Ca and Zn is contained within relative to Mg in solid solution limit, and surplus is by Mg and not
Evitable impurity is constituted, and the content of Zn is more than 0.2 atom % and below 0.4 atom %, and the content of Ca and Zn is with atomic ratio
It is calculated as Ca：Zn=1：(wherein, x is 2~relation 3) to x, and the Mg alloy materials are that average crystallite particle diameter is 20~250 μm
Equi-axed crystal tissue.
During 2~8 weeks of organism soft tissue healing, with reference to keeping organizing, decompose such raw within 1 year or so completely
Decomposition rate in object is most preferred, therefore, it can to make the content of Zn more than 0.2 atom % and below 0.4 atom %,
And meet Ca：Zn=1：The relation of x (wherein x is 2~3).
Organism soft tissue fixation device of the invention, by being made annealing treatment, so as to by average crystallite particle diameter be 20~
250 μm of equi-axed crystal organizational composition, is not only intensity raising and deformation performance is also improved.Average crystallite particle diameter is for example
Can be measured by division lines method by the image of grain structure.
Organism soft tissue of the invention fixes the brake forming for using requirement on devices high, therefore can utilize in deformation midway shape
Into the interface of segmentation grain structure, the i.e. poor (original text of crystalline orientation：Gun parallax) more than 15 ° crystal grain boundary or crystalline orientation it is poor
3 ° of materials less than 15 ° of subgrain interface are constituted.The crystal grain boundary that crystalline orientation differs from more than 15 ° is known as big angle
The interface of crystal boundary is spent, in deformation midway grain structure by obvious Ground Split.Or, even if crystalline orientation difference is less than 15 °, as long as
Subgrain interface, then be divided in deformation midway grain structure.It should be noted that the crystalline orientation at subgrain interface is poor
The reasons why lower limit is set as 3 ° be, as by organize observation can confirm that the limiting value of the crystalline orientation difference of lower limit come
Definition, using with SEM (SEM) it is combined, operation electron ray such that it is able to determine small crystalline orientation,
The EBSD (Electron Back Scatter Diffraction Patterns) of system of crystallization, is set as observable minimum
Value (=3 °).
In addition, it is preferred that be controlled with being heat-treated so that in the crystal grain of Mg alloy materials, can confirm that annealing
Average crystallite particle diameter afterwards is 20~250 μm of equi-axed crystal tissue.Thus, to prevent stress concentration caused by destruction it is related
Connection, can improve the brake forming under normal temperature.Additionally, thus the crystalline structure after shaping is increased by granular with intensity
Advantage.
Organism soft tissue fixation device of the invention is characterised by that the survival rate decomposed in organism is 4 weeks after embedment
It is 50~92%, 2 times of the volume in the space formed when organism is imbedded is not up to the yield of the gas for decomposing
More than.
In addition, organism soft tissue fixation device of the invention is characterised by, can be using the content of Ca and Zn as parameter
To control the decomposition rate in organism.
Then, the preparation method for above-mentioned organism soft tissue fixation device is illustrated.
The preparation method of organism soft tissue fixation device is the device being made up of 3 yuan of the Mg-Ca-Zn Mg alloy materials for being
Preparation method, implement in order it is following 1)~7) the step of.
1) by based on Mg, the content of Zn is below 0.5 atom %, the content of Ca and Zn meets Ca with atomic ratio measuring：Zn=
1：(wherein, x is the mode of 1~relation 3) to x, is added Ca and Zn in solid solution limit in Mg to prepare Mg alloys
The step of material
2) Mg alloy materials are melted and are cast to make the ingot making step of ingot
3) by ingot homogenize heat treatment homogenize heat treatment the step of
4) temperature range at 250~450 DEG C implements the hot-extrudable procedure of processing of hot-extrudable processing at least one times
5) annealing process step of the annealing of 350~450 DEG C of temperature range is carried out
6) it is shaped to the processing and forming step of required device shape
7) the surface removing step of the oxidiferous impurity of bag of device surface is removed
Wherein, above-mentioned annealing process step 5) can be：In hot-extrudable procedure of processing, hot-extrudable temperature is improved, delay heat
Extruded velocity, thus the number after freshly extruded 10 seconds, make ingot be exposed to the condition of high temperature.
In addition, above-mentioned annealing process step 5) is preferably：In Mg alloy materials, based on Mg, the content of Zn is 0.2
More than atom % and 0.4 below atom %, the content of Ca and Zn meet Ca with atomic ratio measuring：Zn=1：X (wherein, x be 2~3)
Relation in the case of, at a temperature of 400 DEG C or so implement 1~8 hour make annealing treatment.
Implement hot-extrudable processing by 250~450 DEG C of temperature range, and can be formed with from sub-micron rank to 10 μm
The equi-axed crystal tissue of the particle diameter of left and right.
In addition, made annealing treatment by 350~450 DEG C of temperature range, and the particle diameter that can be formed after annealing is
20~250 μm of equi-axed crystal tissue.
Annealing is to eliminate the strain of the inside caused by processing hardening, grow grain structure, improves the heat treatment of ductility,
Implement for the sufficient intensity and ductility that obtain needed for being used as clamp.For example, 400 DEG C of temperature is heated to, holding 1~
After the certain hour of 8 hours or so, cooling is placed in an atmosphere.Particle diameter is determined by the image of grain structure by division lines method, also
Other known assay methods can be used.
In addition, instead of implement in 250~450 DEG C of temperature range hot-extrudable processing hot-extrudable procedure of processing and carry out 350~
The annealing process step of the annealing of 450 DEG C of temperature range, it is possible to implement implement heat in 250~400 DEG C of temperature ranges
Extrude the 1st hot-extrudable procedure of processing of processing and at the temperature of procedure of processing more hot-extrudable than the 1st temperature high and 350
Implement the 2nd hot-extrudable procedure of processing of hot-extrudable processing under~450 DEG C of temperature range.By what is carried out at higher temperatures
2nd hot-extrudable procedure of processing, can obtain the effect same with annealing.
It should be noted that 2 stages of the 1st hot-extrudable procedure of processing and the 2nd hot-extrudable procedure of processing are can not be, additionally,
It can be the hot-extrudable procedure of processing in plural stage.In this case, in the hot-extrudable procedure of processing of terminal stage, than preceding rank
The temperature of the hot-extrudable procedure of processing of section is wanted to be processed at temperature high.
In the preparation method of organism soft tissue fixation device of the invention, can by the content of Ca and Zn as a parameter to
Decomposition rate in control organism.
Invention effect
Organism soft tissue fixation device of the invention, only by using magnesium as principal component, by calcium and zinc as addition unit
The necessary element of the organism of element is constituted, therefore in vivo after decomposition it is also ensured that security.Furthermore it is possible to realize following
Effect：With for fixing the intensity and deformation performance of organism soft tissue and decomposition rate can be with suitable control.
Brief description of the drawings
Fig. 1 is 3 yuan of curve maps of the content of the Ca and Zn of the Mg alloy materials for being for representing Mg-Ca-Zn.
Fig. 2 is the Making programme figure of organism soft tissue fixation device.
Fig. 3 is the diagram of strains of the clamp for making.
Fig. 4 is the curve map (1) of the characteristic of the logarithmic strain (true stress) for representing the clamp for implementing annealing.
Fig. 5 is the curve map (2) of the characteristic of the logarithmic strain (true stress) for representing the clamp for implementing annealing.
Fig. 6 is the curve map (3) of the characteristic of the logarithmic strain (true stress) for representing the clamp for implementing annealing.
Fig. 7 is the figure of the crystalline orientation analysis result for representing the clamp for implementing annealing.
Fig. 8 is the curve map of decomposability in the organism for represent the clamp for implementing annealing.
Fig. 9 be implement annealing clamp imbed in vivo after X ray CT cross-sectional image (1).
Figure 10 be implement annealing clamp imbed in vivo after X ray CT cross-sectional image (2).
Figure 11 is the X ray CT cross-sectional image after titanium device (comparative example 1) is imbedded in vivo.
Figure 12 for Zn content more than device (comparative example 2) imbed in vivo after X ray CT cross-sectional image.
Figure 13 is grain structure photo.
Figure 14 is during representing embedment and the curve map (embodiment 3) of volume survival rate.
Figure 15 is the reconstruction image (embodiment 3) of X ray CT cross-sectional image.
Figure 16 is the measure curve map (embodiment 3) of Mg ion concentrations etc. in blood.
Figure 17 is that periphery cell tissue observes result (embodiment 3).
Figure 18 is using the crystalline orientation analysis result (embodiment 4) of EBSD methods.
Figure 19 is the reconstruction image 1 (embodiment 4) of the X ray CT cross-sectional image of rat.
Figure 20 is the reconstruction image 2 (embodiment 4) of the X ray CT cross-sectional image of rat.
Figure 21 is the curve map (4) of the characteristic of the logarithmic strain (true stress) for representing the clamp for implementing annealing.
Figure 22 is the curve map (5) of the characteristic of the logarithmic strain (true stress) for representing the clamp for implementing annealing.
Figure 23 is the curve map (6) of the characteristic of the logarithmic strain (true stress) for representing the clamp for implementing annealing.
Figure 24 is the explanatory diagram (1) of conventional fine grain material.
Figure 25 is the explanatory diagram (2) of conventional fine grain material.
Figure 26 is the true stress-logarithmic strain relation of the pure magnesium of the FEM calculation for representing the clamp for the present embodiment
Curve map.
Specific embodiment
Hereinafter, on one side referring to the drawings, while explaining an example of embodiments of the present invention.It should be noted that
The scope of the present invention is not limited by following embodiment, illustrated example, can carry out numerous variations and deformation.
Embodiment 1
Fig. 1 shows 3 yuan of curve maps of the content of the Ca and Zn of the Mg alloy materials for being for representing Mg-Ca-Zn.For in Fig. 1
Shown 5 samples (Mg alloy materials No.1~No.5), as the evaluation of the serviceability of organism soft tissue fixation device
Result is in following explanation.5 samples (Mg alloy materials No.1~No.5) are as described in Table 1.
[table 1]
Making for 5 samples (Mg alloy materials No.1~No.5) and soft group of the organism using these Mg alloy materials
The preparation method for knitting fixation device, reference picture 2 is illustrated.
First, added with the amount shown in No.1~5 that atomic ratio measuring is above-mentioned table 1 according to the content relative to Mg, Ca and Zn
Plus, prepare Mg alloy materials (S01：Mg alloy materials preparation process).Then, Mg alloy materials are melted and is cast, and made
Ingot (S02：Ingot making step).
Then, ingot is carried out into the heat treatment (S03 that homogenizes：Homogenize heat treatment step).Then, in 300 DEG C of temperature range
Implement hot-extrudable processing (S04：Hot-extrudable procedure of processing), the grain structure granular of inside is made by plastic working.Afterwards, enter
Annealing (the S05 of the temperature range that 400 DEG C of row：Annealing process step).After implementing hot-extrudable processing (S04), further
Keep at high temperature for a long time, it is hereby achieved that the material of homogeneous.
Then, the shape (S06 of the clamp needed for being shaped to：Processing and forming step), the bag for removing clamping surface is oxidiferous
Impurity (S07：Surface removing step).
For the clamp comprising network model for making, the finite element analysis with the Strain Distribution of the fixing phase companion of clamp is carried out.
Fig. 3 is the equivalent plastic strain (original text of clamp 10：Suitable plasticity ひ ず body) distribution map.Diagram of strains shown in Fig. 3
It is using based on pure magnesium (average crystallite particle diameter：47 μm) material data limited element analysis technique result.Wherein, clamp 10
Curve for the true stress-logarithmic strain relation of the pure magnesium of FEM calculation is illustrated in Figure 26.In the curve map of Figure 26
Material is not also broken after dotted line assumes that stress arrival maximum, and turns into the figure of steady state value.The left figure of Fig. 3 represents V words
The clamp (network model before deformation, the open mode before clamping) of shape, right figure represents the state of jaws close.The symbol of Fig. 3
Numbers 11~15 position each represents the deep or light different part on the image of clamp.The bending part 11 of the state of jaws close
It is the maximum position of strain, the order according to 12,13,14 diminishes.The deep or light part of symbol 15 is almost not strain
Part.Result of calculation is that the maximum of equivalent plastic strain is 0.357.Material and shape of 0.357 value according to clamp
Change.But, do not changed because of the size of clamp.Made for being set in pure magnesium material parameter and embodiment
The network model shape of clamp, carries out finite element analysis, in the case where the shape of right figure of Fig. 3 is deformed into, with clamp mould
The maximum of the equivalent plastic strain in type, it is determined that limiting strain necessary to deformation is 0.357.That is, 0.357 value is conduct
One target indicator and the value that sets.Therefore, if the material used in embodiment changes, the Strain Distribution in deformation is also sent out
Changing, thus strain maximum, also changed as the limiting value of target indicator.In the present invention, the shape of clamp,
Size is not limited, therefore on the basis of the strain maximum setting of the clamp of the network model shape that will be used in embodiment.
The clamp of the network model shape for being used in embodiment, it is necessary to use the material not being destroyed in strain more than 0.357
Material.In the clamp of making, at the maximum position 11 of strain, clamp does not occur fracture can be fixed tissue.As described later, it is right
The magnesium alloy made in the present embodiment, obtains showing to compress the material not being broken under caused logarithmic strain 0.357
Experimental result.It follows that the folder constituted using 3 yuan of the Mg-Ca-Zn shown in the present embodiment Mg alloy materials for being
Pincers, can fix organism soft tissue.
Fig. 4 shown for Mg alloy materials No.1 (embodiment A), is represented and is implemented 1 at 350 DEG C of temperature, 400 DEG C, 450 DEG C
The curve map of the characteristic of the logarithmic strain (True strain) of the clamp of the annealing of hour or 8 hours.In the curve map of Fig. 4
In, transverse axis is logarithmic strain (True strain), and the longitudinal axis is true stress (True stress).From the curve map of Fig. 4,
For the clamp being made up of Mg alloy materials No.1 (embodiment A), except the condition of 8 hours 1 hour at 350 DEG C, at 450 DEG C
Situation, even if producing more than 0.357 strain, is not also broken.I.e., in the case of as little as 350 DEG C of annealing temperature, 1 hour
Heat treatment in, the coarsening of crystal grain is insufficient, it is necessary to implement the heat treatment of 8 hours.In addition, in up to 450 DEG C of annealing temperature
In the case of, the heat treatment of 1 hour is enough, the crystalline structure of the strain of the essential value more than 0.357 that can be eliminated.With
This is relative, and in the heat treatment of 8 hours, crystalline structure occurs required degree with Shangdi coarsening, therefore cannot eliminate essential value
More than 0.357 strain.Thus, most suitable annealing region and retention time scope are implied the presence of.
Fig. 5 shown for Mg alloy materials No.5 (comparative example), is represented and is implemented 1 at 350 DEG C of temperature, 400 DEG C, 450 DEG C
The curve map of the characteristic of the logarithmic strain (True strain) of the clamp of the annealing of hour or 8 hours.By the curve map of Fig. 5
Understand, the clamp being made up of Mg alloy materials No.5 (comparative example) has no the data of the strain for eliminating essential value more than 0.357
Repeatability.
Fig. 6 show represent the clamp that is constituted with Mg alloy materials No.1 (embodiment A) implemented at 400 DEG C 1 hour, 2
The curve map of the characteristic of the logarithmic strain (True strain) of the clamp of the annealing of 4 groups of hour, 4 hours, 8 hours.By
The curve map of Fig. 6 understands that the clamp being made up of Mg alloy materials No.1 (embodiment A) has in the case of annealing 8 is small
Situation and the situation of reduction that the characteristic of logarithmic strain (True strain) is improved.In the material of Mg alloy materials No.1, calcium and
The concentration of main solute atoms is low as zinc, thus annealing time be set to 8 it is small in the case of, it is believed that solute atoms institute
Pinning (the original text of the crystal boundary of cause：ピ Application stops め) effect reduction, the easy coarsening of partially crystallizable tissue.Such case hint,
In the case that solute atoms concentration is low when annealing time is long, possibly essential value cannot be met.Such case is implied, for annealing
, there is the retention time scope being best suitable in treatment.
Wherein, even if the grain structure of the material for producing more than 0.357 strain not also to be broken is illustrated.Figure 13
(1)~(3) represent for Mg alloy materials No.1 (embodiment A) respectively, implement 8 hours at 350 DEG C of temperature, at 400 DEG C
Under implement 2 hours, implement at 450 DEG C 1 hour annealing clamp grain structure photo.It is real at 350 DEG C
The clamp such as Fig. 4 and Fig. 6 for the annealing for applied 8 hours, implementing at 400 DEG C 2 hours, implement at 450 DEG C 1 hour
It is shown, though produce more than 0.357 strain do not occur yet fracture (at 350 DEG C 8 hours reference pictures 4,2 hours at 400 DEG C
Reference picture 6,1 hour reference picture 4 at 450 DEG C).Moved back it has been confirmed that implementing by the grain structure photo of Figure 13 (1)~(3)
It is 20 μm or so if the particle diameter of the clamp of fire treatment is small, is greatly 250 μm or so.
Figure 21 show represent the clamp that is constituted with Mg alloy materials No.2 (embodiment B) implemented at 400 DEG C 1 hour, 2
The curve map of the characteristic of the logarithmic strain (True strain) of the clamp of the annealing of 4 groups of hour, 4 hours, 8 hours.By
The curve map of Figure 21 is it has been confirmed that in the clamp being made up of Mg alloy materials No.2 (embodiment B), implement 4 hours or 8
Situation and the situation of reduction that the characteristic that the clamp of the annealing of hour has logarithmic strain (True strain) is improved, but
The characteristic that confirmation implements the logarithmic strain (True strain) of the clamp of the annealing of 1 hour or 2 hours is improved.This
The situation of kind is implied, in the clamp being made up of Mg alloy materials No.2 (embodiment B), there is most suitable guarantor for annealing
Hold time range.
Figure 22 show represent the clamp that is constituted with Mg alloy materials No.3 (embodiment C) implemented at 400 DEG C 1 hour, 2
The curve map of the characteristic of the logarithmic strain (True strain) of the clamp of the annealing of 4 groups of hour, 4 hours, 8 hours.By
The curve map of Figure 22 is implemented 4 hours and 8 small it has been confirmed that in the clamp being made up of Mg alloy materials No.3 (embodiment C)
When the clamp of annealing there is the characteristic situation about improving and situation about reducing of logarithmic strain (True strain), but really
The characteristic for recognizing the logarithmic strain (True strain) of the clamp of the annealing for implementing 1 hour or 2 hours is improved.It is this
Situation is implied, in the clamp being made up of Mg alloy materials No.3 (embodiment C), when there is most suitable holding for annealing
Between scope.
Figure 23 show represent the clamp that is constituted with Mg alloy materials No.4 (embodiment D) implemented at 400 DEG C 1 hour, 2
The song of the characteristic of the logarithmic strain (True strain) of the clamp of the annealing of 5 groups of hour, 3 hours, 4 hours, 8 hours
Line chart.By the curve map of Figure 23 it has been confirmed that in the clamp being made up of Mg alloy materials No.4 (embodiment D), implementing 3 hours
The characteristic of the logarithmic strain (True strain) of the clamp of annealing is improved.In addition, confirmation is implemented at the annealing of 4 hours
Situation and the situation of reduction that the characteristic that the clamp of reason has logarithmic strain (True strain) is improved.But, confirm to implement
The clamp of the annealing of 1 hour, 2 hours and 8 hours has no the reproduction of the data of the strain for eliminating essential value more than 0.357
Property.Imply in the clamp being made up of Mg alloy materials No.4 (embodiment D), exist most for annealing by these situations
Suitable retention time scope.
Then, for made clamp, using with SEM (SEM) is combined, operation electron ray and can be with
Small crystalline orientation, the EBSD of system of crystallization is determined, crystalline orientation analysis is carried out, for the result for having parsed plastic deformation behavior
Illustrate.
Fig. 7 (1) (2) represents the crystalline orientation analysis result of the cylinder test film for implementing annealing.Fig. 7 (1) is represented Mg
Alloy material (No1：Embodiment A) it is compressed to load removal after logarithmic strain 0.123 and the crystalline substance inside the compression test piece for reclaiming
Grain institutional framework, Fig. 7 (2) is represented will be by Mg alloy materials (No1：Embodiment A) constitute cylinder test film be compressed to truly should
The grain structure structure of the inside of load removal and the compression test piece for reclaiming after the compression of change 0.193.Grain structure structure should
The value of change is calculated as follows：" the relation of load-displacement as obtained from the compression test by the cylinder test film of respective state
(curve) ", obtains " nominal stress (Nominal stress：σn)-apparent strain (Nominal strain：εn) relation it is (bent
Line) ", by " true stress (True stress：σt=σn(1-εn))-logarithmic strain (True strain：εt=-ln (1-
εn)) relation (curve) " calculate.Here, nominal stress is the value that load is obtained divided by initial stage sectional area, apparent strain is
The value that (height after the initial stage height-deformation of test film) is highly obtained divided by the initial stage of test film.
The state of the jaws close shown in Fig. 7 (2), i.e. deformation midway Mg alloy materials crystal grain in, confirm every several μm
Interface with misorientation for several times.From such case, by the formation of submicron particle (subgrain), Accompanying Deformation, accumulation
Strain disappear, there is so-called dynamic recovery, so as to avoid the formation of crackle (trickle cracking) caused by stress concentration, have
Help improve ductility.
Fig. 8 is to represent the curve map for implementing the clamp of annealing decomposability in vivo.This is to imitate body fluid
Solution (E-MEM：10%FBS, CO2Concentration：5%, 37 DEG C) the middle result of the test for impregnating the in vitro that certain hour is obtained.
The left side of the curve map of Fig. 8 represents for Mg alloy materials No.1~No.3, structure and identical environment in organism, makes
By the volume survival rate of the clamp after 4 weeks in environment is stood, the right side of curve map represents for Mg alloys the clamp of making
Material No.1 and No.2, build with identical environment in organism, the clamp of making is put in the above-mentioned solution for slowly flowing back
Put 4 weeks, the i.e. survival rate of the clamp after circulation environment decentralization puts 4 weeks.Here, volume survival rate is set to that image will be observed with CT
The remaining volume of the magnesium alloy for calculating is divided by result, the ratio tried to achieve obtained by the volume before dipping.
From the curve map of Fig. 8, the volume survival rate under standing environment by the clamp after 4 weeks is all more than 90%, is circulated
Survival rate under environment by the clamp after 4 weeks is all more than 85%, used as the organism of organism soft tissue fixation device
Interior decomposition rate is appropriate.If in addition, being tried using the in vitro of the dipping certain hour in the solution of above-mentioned imitation body fluid
Proved recipe method, then the order volume according to Mg alloy materials No.1 (embodiment A), No.2 (embodiment B), No.3 (embodiment C) is residual
The rate of depositing increases, therefore, it is known that decomposition rate sequentially delays according to this in organism.In addition, from such case, in organism
Decomposition rate can be adjusted with the concentration of Ca and Zn.
As described above, substantially can be used as organism soft tissue fixation device using the device of Mg alloy materials No.1~No.3.
Embodiment 2
In embodiment 2, carried out really for decomposability in organism of the organism soft tissue fixation with device that makes and security
Recognize, thus it is as described below.
Fig. 9 and Figure 10 represent that the organism of preparation method similarly to Example 1, the U-shaped for implementing annealing is soft
X ray CT cross-sectional image after in the fixed organism with device embedment mouse of tissue.
Organism soft tissue fixation device is tieed up after embedment by behind 7 days, 14 days, 28 days, being confirmed by X ray CT cross-sectional image
The shape of U-shaped is held.
Fig. 9 (1) be embedment mouse after by the image after 7 days.Fig. 9 (2) be embedment mouse after by the image after 14 days.It is any
In the case of, the change of the volume in space from after just embedment is small, thus it is confirmed that the yield of gas extremely pettiness, not
It was found that gas drastically is produced.
Figure 10 (1) is the reconstruction image for just having imbedded the X ray CT cross-sectional image after mouse.Figure 10 (2) be embedment mouse after by
The reconstruction image of the X ray CT cross-sectional image after 28 days.From the device shape rebuild, by after 28 days, confirming by equal
Volume is reduced caused by even decomposition, but maintains the shape of U-shaped.It follows that partly not there is defect in device, dimension
Conclusion performance in during having held.It should be noted that perienchyma when observing X ray CT by visual observation and taking out, not
It was found that lesion.
Here, used as comparative example, the device (comparative example 2) more than titanium device (comparative example 1) and the content of Zn is in organism
Interior decomposability is described.
Figure 11 represent titanium device (comparative example 1) imbed in vivo after X ray CT cross-sectional image.In addition, Figure 12 is represented
The content of Zn be 6 atom % device (comparative example 2) imbed in vivo after X ray CT cross-sectional image.
Understood in the case of titanium device (comparative example 1), after embedment mouse, by still maintaining undecomposed shape (ginseng after 28 days
According to Figure 11).It should be noted that not shown in figure, but in the case of titanium device (comparative example 1), in X ray CT cross-sectional image
Artifact influence it is big, it may be said that be difficult to the observation of bio-tissue.
On the other hand, come for the Mg alloy materials containing zinc to 6 atom % greatly for amount, the decomposition rate in organism is fast,
Therefore by after 7 days, being decomposed with organism, substantial amounts of gas (hydrogen) is produced.After Figure 12 (1) expression embedment mouse, by 7
X ray CT cross-sectional image in the future.In Figure 12 (1), the black space of the vestige being detained with the gas represented after device disappearance
Region, the edge of area of space has bright part, can confirm that metal structure, the bone as remaining clamp.
In addition, by after 14 days, metal structure is decomposed completely, being changed into the chemical combination of calcium phosphate, magnesium phosphate, magnesium carbonate, calcium carbonate etc.
Thing, the corrosion product of remaining device in the organism of mouse.After Figure 12 (2) expression embedment mouse, by the X-ray after 14 days
CT cross-sectional images.Corrosion product forms the contrast lower than bone, therefore is embedded in soft tissue and is difficult to decompose, can be true in Figure 12 (2)
Recognize the part of corrosion product (calcium phosphate, magnesium phosphate, magnesium carbonate, calcium carbonate).
Compared with the rheological parameters' change with time of the material of the comparative example 1,2 of above-mentioned 2 species, it is known that organism soft tissue of the invention is fixed and used
Device has the effect of the delay of the organized renewing that can avoid producing with a large amount of gases, appropriate period in vivo
Conclude and keep performance, for the less harmful of organism.
Embodiment 3
＜ is in the subcutaneous embedment experiment ＞ of mouse web portion
First, illustrate to be embedded to the clamp (the hereinafter referred to as clamp of the present embodiment) made in method same as Example 2
The result of the subcutaneous experiment of mouse web portion.Used as comparative example, the content for titanium clamp (comparative example 1) and Zn is 6 atom %
Clamp (comparative example 2), it is subcutaneous to be similarly embedded to mouse web portion, is tested.
Visual inspection is carried out, is imbedded by after 1 week, the clamp (comparative example 1) of clamp and titanium for the present embodiment does not find
Gas produce caused by space growth, but the clamp of comparative example 2 more than content for Zn finds the growth in big space.Recognize
For this is because, in the clamp of comparative example 2 more than the content of Zn, decomposition rate is fast in organism, thus by after 1 week with raw
Decomposed in object and produce substantial amounts of gas (hydrogen).
Figure 14 is during embedment is represented for the clamp of the present embodiment and the curve map of volume survival rate.Curve map is to being used for
Obtained by the average value of 3 mouse of experiment is drawn.As shown in figure 14, the clamp of the present embodiment in mouse organism with
The time passage and volume reduce, 1 month after embedment (by after 4 weeks) be 70%, (by after 12 weeks) 3 months after embedment
It is 50%.
Figure 15 (a)~(e) each represent embedment mouse after by after 1 week, by after 2 weeks, by after 3 weeks, by after 4 weeks, warp
After the reconstruction image of the X ray CT cross-sectional image of the clamp of the present embodiment after 12 weeks.Confirmed by Figure 15, the clamp of the present embodiment
At at the time point by 12 weeks, the shape of clamp when remaining embedment.
Then, show to determine the result of Mg ion concentrations etc. in the blood in the organism after embedment untill after 12 weeks.Under
State and represent measure object in table 2.In addition, the data checked for serum, carry out analysis statistically.It should be noted that
Analysis statistically is, it is assumed that data are normal distribution, by F test and judges dispersiveness, then, for the number of homoscedasticity
Checked according to using student t, for the data of heteroscedasticity, checked using Welch t, so as to be analyzed, by all analyses
Significance be set as p ＜ 0.05.
[table 2]
The song of the measurement result of Mg ion concentrations etc. in the blood in the organism after embedment untill after 12 weeks is represented in Figure 16
Line chart.Each graphical representation of Figure 16 (1)~(5) is for the clamp (the present embodiment), titanium clamp (comparative example 1) and the Zn that make
Many clamp (comparative example 2) each, by after 1 week, by after 2 weeks, by after 3 weeks, by after 4 weeks, by after 12 weeks
The numerical value of Mg, CRE, AST, ALP and ALT.In bar chart, by by the data after the stipulated time according to comparative example 1, comparative example
2nd, from left to right 3 bar shapeds each show the order of the present embodiment side by side.In addition, the bar shaped of the right-hand member of each curve map is not cut open
Abdomen does not imbed the normal mouse of anything as control yet, shows by the numerical value after 4 weeks.It should be noted that curve
The data of figure are 3 average values of the data of mouse.
It is unconfirmed to concentration significance by the result of Mg ion concentrations in the blood after the embedment that determines untill after 12 weeks
Ground increases, thus it is confirmed that released ion is excreted.
Figure 17 show embedment after by the periphery after 2 weeks cell tissue observation result.Figure 17 (1)~(3) expression, for
Clamp (the present embodiment), each clamp of clamp (comparative example 2) more than titanium clamp (comparative example 1) and Zn for making are imbedded
Periphery cell tissue, implements and dyes (HE dyeing) and Picro-Sirius red with haematine (Haematoxylin) eosin (Eosin)
The result (left image is HE dyeing, right image for SR is dyeed) of the SR dyeing of (Sirius red).
The cell tissue on the periphery of the clamp (the present embodiment) made according to embedment and the periphery of embedment titanium clamp (comparative example 1)
Cell tissue cell observation, do not find inflammatory reaction, periphery cell tissue is normal, confirms the clamp of the present embodiment
Organism security.On the other hand, in the cell tissue observation on the periphery of the clamp (comparative example 2) more than embedment Zn, confirm not
It was found that fibrous form, intercellular matrix (cell membrane) is destroyed, and the core in cell is not formed, the feelings that necrosis occurs
Condition.
Embodiment 4
＜ tests ＞ using the vascular anastomosis of rat
In example 4, the preparation method from embodiment 2 and the clamp of embodiment 3 is different, in hot-extrudable procedure of processing, carries
Hyperpyrexia extrusion temperature, delays hot-extrudable speed, and thus the number after just completion extrusion makes ingot be exposed to high temperature shape between 10 seconds
State, carries out annealing process step after just hot-extrudable procedure of processing is carried out, and makes clamp, for made clamp, confirms
Decomposability and security, are described as follows in organism.
For the clamp of embodiment 4, using the Zn and Ca of the Mg alloy materials of the No.1 in the above-mentioned table 1 shown in embodiment 1
Content.More specifically, relative to the atom % of Mg 99.69, the Zn of the Ca and 0.21 atom % of 0.1 atom % is added, is carried out
Melt and cast, make ingot, the ingot is carried out into the heat treatment that homogenizes.Ingot after heat treatment is implemented the 1st at 350 DEG C
The hot-extrudable processing in stage, diameter 22mm is processed into by the ingot of diameter 90mm.Machining is carried out to diameter 22mm, is made straight
Footpath 20mm, implements the hot-extrudable processing of the 2nd stage at 410 DEG C, is processed into V-type section.Just complete the 2nd stage it is hot-extrudable it
Afterwards, number 10 seconds at 400~410 DEG C, are made annealing treatment.Then, the oxidiferous impurity of bag of clamping surface is removed.
For make clamp, using with SEM (SEM) it is combined, operation electron ray it is micro- such that it is able to determine
Small crystalline orientation, the EBSD of system of crystallization, carries out crystalline orientation analysis, shows the result in Figure 18.Crystallization as shown in Figure 18 takes
Confirm that the crystalline structure of the clamp of making is equi-axed crystal tissue to analysis result.In addition, to the clamp made using microtomy
The average crystallite particle diameter of crystalline structure be measured, be 28.8 (μm) near the V words bottom of clamp, in V word near tops
It is 31.5 (μm).
Confirm average crystallite particle diameter substantially 30 (μm) of the clamp of making, be equi-axed crystal tissue.Closed by the V words of the clamp
In the state of conjunction, as shown in Figure 7, occur the often several μm of interfaces with misorientation for several times in crystal grain and (form sub-
Grain), Accompanying Deformation, the strain of accumulation disappears, it is to avoid the formation (mitigation of stress concentration) of crackle caused by stress concentration, therefore
With excellent deformation performance.
Then, the clamp of use, the blood vessel and bile duct that the part with the liver of rat is connected is coincide, for knot
Fruit illustrates.The blood vessel and bile duct that are connected with a part for liver are combined, the abdominal incision of rat by the folder of V shape
Icarceration is closed and coincide.Then, hepatectomize.
After excision by after 1 week and by the rat after 4 weeks (1 month) chest X ray CT cross-sectional image reconstruction image
As shown in figure 19.In Figure 19, (1) represent excision after by after 1 week, (2) represent excision after by the weight after 4 weeks (1 month)
Build image.In Figure 19 (1) (2), (a) is coincide with the clamp of the present embodiment, and (b) is carried out with the clamp of comparative example 1
It coincide.
As shown in figure 19, after hepatotomy, i.e. blood vessel and bile duct cut-out after, still survived by rat after 4 weeks, and
Find to be produced without substantial amounts of gas using X ray CT, and do not find clamp opening, thereby it is assumed that to maintain and expected
Clamp conclusion performance.
In addition, being contemplated to, clamp is equably decomposed in the organism of rat, maintain to conclude during certain performance it
Afterwards, finally it is decomposed and is discharged.Thus, confirm that decomposability clamp in the organism with security can be realized.
Figure 20 represents the X ray CT cross-sectional image of rat.In Figure 20, (1) is after a resection by the X ray CT section after 1 week
Image, (2) are after a resection by the X ray CT cross-sectional image after 4 weeks (1 month).Figure 20 (1) (2) is represented and implemented with this
The clamp of example carries out identical situation.For the clamp of the present embodiment, it is known that：It is difficult to produce during using conventional titanium clamp
Metal artifacts when X ray CT is imaged, without image correction, can clearly observe bio-tissue.
Industrial applicability
Organism soft tissue fixation device of the invention can be combined and protected during 2~8 weeks that organism soft tissue heals
Tissue is held, was decomposed completely at 1 year or so, be then discharged, therefore can be used for surgical operation clamp, stapler etc..
Symbol description
10 clamps
Claims (9)
1. a kind of organism soft tissue fixation device, it is characterised in that be the Mg alloy material structures for being by 3 yuan of Mg-Ca-Zn
Into device,
On the Mg alloy materials,
Ca and Zn are contained within solid solution limit relative to Mg, surplus is made up of Mg and inevitable impurity, the content of Zn
It is below 0.5 atom %, the content of Ca and Zn is with atomic ratio measuring as Ca：Zn=1：The relation of x, wherein, x is 1~3,
The Mg alloy materials are the equi-axed crystal tissues that average crystallite particle diameter is 20~250 μm.
2. a kind of organism soft tissue fixation device, it is characterised in that be the Mg alloy material structures for being by 3 yuan of Mg-Ca-Zn
Into device,
On the Mg alloy materials,
Ca and Zn are contained within solid solution limit relative to Mg, surplus is made up of Mg and inevitable impurity, the content of Zn
It is more than 0.2 atom % and below 0.4 atom %, the content of Ca and Zn is with atomic ratio measuring as Ca：Zn=1：The relation of x, wherein,
X is 2~3,
The Mg alloy materials are the equi-axed crystal tissues that average crystallite particle diameter is 20~250 μm.
3. organism soft tissue fixation device as claimed in claim 1 or 2, it is characterised in that formed point in deformation midway
Cut the interface of the grain structure, i.e. crystalline orientation differ from more than 15 ° of crystal grain boundary or crystalline orientation differ from 3 ° less than
15 ° of subgrain interface.
4. the organism soft tissue fixation device as any one of claims 1 to 3, it is characterised in that in organism
The survival rate of decomposition was 50~92% at 4 weeks after embedment, and organism embedment is not up to the yield of the gas for decomposing
When formed more than 2 times of the volume in space.
5. the organism soft tissue fixation device as any one of Claims 1 to 4, it is characterised in that by the Ca
With the content of Zn as parameter, the decomposition rate in control organism.
6. a kind of preparation method of organism soft tissue fixation device, it is characterised in that be by 3 yuan of Mg for being of Mg-Ca-Zn
The preparation method of the device that alloy material is constituted, possesses following steps：
By based on Mg, the content of Zn is below 0.5 atom %, the content of Ca and Zn meets Ca with atomic ratio measuring：Zn=1：x
Relation mode, the step of Ca and Zn is added in solid solution limit to prepare Mg alloy materials in Mg, wherein, x
It is 1~3；
Mg alloy materials are melted and cast, the ingot making step of ingot is made；
By ingot homogenize heat treatment homogenize heat treatment the step of；
Implement the hot-extrudable procedure of processing of hot-extrudable processing at least one times in 250~450 DEG C of temperature ranges；
Carry out the annealing process step of the annealing of 350~450 DEG C of temperature range；
It is shaped to the processing and forming step of required device shape；With
Remove the surface removing step of the oxidiferous impurity of bag of device surface.
7. a kind of preparation method of organism soft tissue fixation device, it is characterised in that be by 3 yuan of Mg for being of Mg-Ca-Zn
The preparation method of the device that alloy material is constituted, possesses following steps：
By based on Mg, the content of Zn is below 0.5 atom %, the content of Ca and Zn meets Ca with atomic ratio measuring：Zn=1：x
Relation mode, the step of Ca and Zn is added in solid solution limit to prepare Mg alloy materials in Mg, wherein, x
It is 1~3；
Mg alloy materials are melted and cast, the ingot making step of ingot is made；
Ingot homogenize the heat treatment step that homogenizes of heat treatment；
Implement the 1st hot-extrudable procedure of processing of hot-extrudable processing in 250~400 DEG C of temperature ranges；
Implement heat at the temperature of procedure of processing more hot-extrudable than the 1st temperature high and under 350~450 DEG C of temperature range
Extrude the 2nd hot-extrudable procedure of processing of processing；
It is shaped to the processing and forming step of required device shape；With
Remove the surface removing step of the oxidiferous impurity of bag of device surface.
8. the preparation method of organism soft tissue fixation device as claimed in claims 6 or 7, it is characterised in that will be described
The content of Ca and Zn is used as parameter, the decomposition rate in control organism.
9. the preparation method of organism soft tissue fixation device as claimed in claim 6, it is characterised in that closed in the Mg
In golden material, relative to Mg, the content of Zn is more than 0.2 atom % and below 0.4 atom %, and the content of Ca and Zn is with atomic ratio
Meter meets Ca：Zn=1：The relation of x, wherein, when x is 2~3,
Temperature of the annealing process step near 400 DEG C is implemented to make annealing treatment for 1~8 hour.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-183716 | 2014-09-09 | ||
| JP2014183716 | 2014-09-09 | ||
| JP2015050101 | 2015-03-12 | ||
| JP2015-050101 | 2015-03-12 | ||
| PCT/JP2015/004596 WO2016038892A1 (en) | 2014-09-09 | 2015-09-09 | Device for fixing biological soft tissue, and method for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106715737A true CN106715737A (en) | 2017-05-24 |
| CN106715737B CN106715737B (en) | 2018-12-04 |
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|---|---|---|---|
| CN201580048143.2A Active CN106715737B (en) | 2014-09-09 | 2015-09-09 | Fixed device of organism soft tissue and preparation method thereof |
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| Country | Link |
|---|---|
| US (1) | US10994056B2 (en) |
| EP (1) | EP3192886B1 (en) |
| JP (2) | JP6164675B2 (en) |
| KR (1) | KR102227158B1 (en) |
| CN (1) | CN106715737B (en) |
| AU (2) | AU2015313647B2 (en) |
| CA (1) | CA2960612C (en) |
| ES (1) | ES2706890T3 (en) |
| MY (1) | MY183300A (en) |
| PL (1) | PL3192886T3 (en) |
| RU (1) | RU2688064C2 (en) |
| SG (1) | SG11201701814TA (en) |
| WO (1) | WO2016038892A1 (en) |
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| CN111534769A (en) * | 2020-03-03 | 2020-08-14 | 李贺杰 | Heat treatment method for improving mechanical property and biological function stability of magnesium alloy |
| WO2021174998A1 (en) * | 2020-03-03 | 2021-09-10 | 李贺杰 | Method for increasing mechanical performance and biological stability of magnesium alloy and for manufacturing material and applications |
| CN113840939A (en) * | 2019-05-20 | 2021-12-24 | 大众汽车股份公司 | Sheet metal product with high bendability and manufacturing method thereof |
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| US10994056B2 (en) * | 2014-09-09 | 2021-05-04 | National University Corporation Kobe University | Device for fixing biological soft tissue, and method for producing same |
| JP6774787B2 (en) * | 2016-05-25 | 2020-10-28 | 権田金属工業株式会社 | Magnesium alloy manufacturing method |
| CN108330368B (en) * | 2018-03-30 | 2024-06-18 | 西安卓恰医疗器械有限公司 | Biological implant, components thereof and preparation method thereof |
| CN113164659B (en) * | 2018-11-30 | 2023-08-25 | 尤安艾公司 | biodegradable metal alloy |
| KR102095813B1 (en) * | 2019-11-28 | 2020-04-03 | 유앤아이 주식회사 | Method for manufacturing biodegradable metal alloy |
| EP4215222A1 (en) * | 2020-11-04 | 2023-07-26 | Korea Institute Of Materials Science | High-strength, high-anticorrosive, biodegradable magnesium alloy and implant using same |
| KR102674799B1 (en) * | 2020-11-04 | 2024-06-17 | 한국재료연구원 | Biodegradable magnesium alloy with high strength and high corrosion resistance and implants using the same |
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Also Published As
| Publication number | Publication date |
|---|---|
| PL3192886T3 (en) | 2019-05-31 |
| KR20170053640A (en) | 2017-05-16 |
| JP6164675B2 (en) | 2017-07-19 |
| JPWO2016038892A1 (en) | 2017-04-27 |
| EP3192886A4 (en) | 2017-08-30 |
| WO2016038892A1 (en) | 2016-03-17 |
| US20170258968A1 (en) | 2017-09-14 |
| RU2688064C2 (en) | 2019-05-17 |
| US10994056B2 (en) | 2021-05-04 |
| CN106715737B (en) | 2018-12-04 |
| RU2017111570A (en) | 2018-10-11 |
| CA2960612C (en) | 2020-10-27 |
| RU2017111570A3 (en) | 2019-03-26 |
| MY183300A (en) | 2021-02-18 |
| EP3192886B1 (en) | 2018-10-17 |
| CA2960612A1 (en) | 2016-03-17 |
| SG11201701814TA (en) | 2017-04-27 |
| JP2017197846A (en) | 2017-11-02 |
| AU2015313647B2 (en) | 2020-04-09 |
| AU2015313647A1 (en) | 2017-03-23 |
| KR102227158B1 (en) | 2021-03-11 |
| AU2020204559A1 (en) | 2020-07-30 |
| EP3192886A1 (en) | 2017-07-19 |
| ES2706890T3 (en) | 2019-04-01 |
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